Organotin miticidal and insecticidal compounds

ABSTRACT

A COMPOSITION OF MATTER IS DESCRIBED HEREIN WHICH HAS INSECTICIDAL AND MITICIDAL ACTIVITY AND METHODS OF USE. THE COMPOSITION MAY BE DEFINED BY THE FOLLOWING GENERIC FORMULA   R1-P(=S)(-R2)-S-SN(CYCLOHEXYL)3   WHEREIN R1 IS LOWER ALKYL HAVING 1 TO 4 CARBON ATOMS, AND R2 CAN BE SELECTED FROM ALKYLALDKOXIMINO, PIPERIDYL, CYCLOALKYLKETOXIMINO, ALKYLALDOXIMINO, ALKYLCARBAMYLALKOXY, HEXAMETHYLENEIMINO, ALKYLOXAZOLIDINE, AND   -N(-R3)-R4   WHEREIN R3 AND R4 CAN BE THE SAME OF DIFFERENT AND CAN BE SELECTED FROM HYDROGEN, ALKYL HAVING 1 TO 15 CARBON ATOMS, ALKOXYALKYL, ALKENYL, BENZYL, CYANOALKYL, ALKANOL, PHENYL, ALKYLPHENYL, SULFONAMIDOPHENYL, THIAZOLINYL, ALKOXYCARBAMYL, HALOBENZYL, FURFURYL, PROVIDED THAT WHEN R3 IS HYDROGEN, R4 IS OTHER THAN HYDROGEN.

United States Patent ome 3,832,370 Patented Aug. 27, 1974 ABSTRACT OF THE DISCLOSURE A composition of matter is described herein which has insecticidal and miticidal activity and methods of use. The composition may be defined by the following generic formula /CHg-CH1 CH2 H CH1-C 1 alkoxy, hexamethyleneimino,

wherein R is lower alkyl having 1 to 4 carbon atoms, and

R can be selected from alkylketoximino, piperidyl, cycloalkylketoximino, alkylaldoximino, alkylcarbamylalkoxy, hexamethyleneimino, alkyloxazolidine, and

wherein R and -R., can be the same or difierent and can be selected from hydrogen, alkyl having 1 to 15 carbon atoms, alkoxyalkyl, alkenyl, benzyl, cyanoalkyl, alkanol, phenyl, alkylphenyl, sulfonamidophenyl, thiazolinyl, alkoxycarbamyl, halobenzyl, furfuryl, provided that when R is hydrogen, R is other than hydrogen.

BACKGROUND OF THE INVENTION BRIEF DESCRIPTION OF THE INVENTION It has been discovered that certain organotin compounds have relatively low phytotoxicity properties and are relatively stable. These organotin compounds may be defined by the following generic formula GHQ-CHI CI'Ir-CH,

GH -C t- 2 Cm C GHQ-C 1 wherein R, is lower alkyl having 1 to 4 carbon atoms,

and R can be selected from alkylketoximino, piperidyl, cycloalkylketoximino, alkylaldoximino, alkylcar-bamylalkyloxazolidine, and

- wherein R and R, can be the same or different and can be selected from hydrogen, alkyl having 1 to 15 carbon atoms, alkoxyalk-yl, alkenyl, benzyl, cyanoalkyl, alkanol, phenyl, alkylphenyl, sulfonamidophenyl, thiazolinyl, alkoxycarbamyl, halobenzyl, furfuryl, provided that when R, is hydrogen, R is other than hydrogen.

DETAILED DESCRIPTION OF THE INVENTION In the practice of the present invention, the compounds of the present invention are manufactured by reacting an alkylthiophospl ine sulfide with an appropriate amine in a neutral sol'ventvtoform an intermediate compound. The intermediatecompound is then reacted with an alkyl tin halide'to form the end product. The halide moiety in the allgyl tin halidecan be selected from the group consisting of chlorine, bromine and iodine. After the compounds of the present invention are formed, they can be applied to the habitat in an effective amount to control respective mites and insects.

The following examples illustrate the merits of the present invention: i

Example 1 (Q) a H(CHz)nCH A mixture was formed containing 2.2 grams (0.009 mole) of ethylthiophosphine sulfide, 50 ml. of tetrahydrofuran, 2.8 grams (0.015 mole) of dodecylamine and 7.0 ml. of triethylamine. This mixture was allowed to stand for 1 hour wherein 6.1 grams (0.015 mole) of tricyclohexyl tin chloride was added and the mixture was allowed to stand for 24 hours. Then, the mixture was heated to boiling for a few minutes, then diluted with 100 ml. of chloroform, washed with 100 ml. of, water and 50 ml. of

sodium bicarbonate solution, dried over magnesium sulfate and evaporated in vacuo to yield 6.5

d t grams of pro uc Example 2 3 C211: ...t r a Nncmcmocm A'mixture was. formed containing 2.2 grams (0.009

r mole) of ethylthiophosphine sulfide, 50 ml. tetrahydro furan, and 3.0 grams (0.04 mole) of inethoxyethylamine.

Themixtureiwas' allowed to stand for 1 hour, wherein 6.1 grams (0.015 mole) of tiicyclohexyl tin chloride was added. Themixture Was allowed to stand for 24 hours. Then, the mixture was heated to boiling for a few min utes, diluted'with ml. of chloroform, washed with .3 100 ml. of water and a 50 ml. solution of sodium bicarbonate, dried over magnesium sulfate and evaporated in vacuo to yield 6.5 grams of product, mp. 56-59" C.

Example 3 A mixture was formed containing 2.2 grams (0.009 mole) of ethylthiophosphine sulfide, 50 m1. of ethyl ether and 4.1 ml. (0.04 mole) of, diethylamine. This mixture was allowed to stand for 1 hour. Then, 6.1 grams (0.015 mole) of tricyclohexyl tin chloride and 50 ml. tetrahydrofuran was added and the mixture was allowed to stand for 24 hours. Then, the mixture was boiled for a few minutes, diluted with 50 ml. of ethyl ether and then washed with 100 ml. of water, 50 ml. of a saturated solution of sodium bicarbonate, dried over magnesium sulfate and evaporated in vacuo to yield 7.0 grams of product.

Example 4 S H (Q) A mixture was formed containing 2.2 grams (0.009 mole) of ethylthiophosphine sulfide, 50 ml. tetrahydrofuran, 1.70 grams (0.015 mole) of cyclohexanoneoxime and 7.0 ml. of triethylamine. This mixture reacted exothermically with the addition of triethylamine. After 1 hour, 6.0 grams (0.015 mole) of tricyclohexyl tin chloride was added and allowed to stand for 2 days. The mixture was diluted with 100 ml. of cholroform. The mixture was then washed with 100 m1. of water, 50 ml. of saturated sodium bicarbonate solution, dried over magnesium sulfate and evaporated in vacuo to yield an oil that was triturated with methanol to yield 7.2 g. of crystals, m.p. 76-79 C.

Example S 0 H (cr t The procedure of Example 4 was repeated in its entirety except 1.8 grams (0.019 mole) of aniline was substituted for the 1.70 grams of cyclohexanoneoxime. The yield was 6.0 grams of product, m.p. 88-90 C.

Example 6 Susi (O1 NHNniiooH.

The procedure of Example 4 was repeated in its entirety except 1.37 grams (0.015 mole) of methylhydrazinocarboxylate was substituted for the 1.70 grams of cyclohexanoneoxime and only a 24 hour reaction period was used instead of 2 days. The yield was 5.0 grams of product, mp. 83-86 C.

Example 7 S CsHa nrrouzcmomoni Example 8 N HCHa The procedure of Example 7 was repeated in its entirety except 1.1 grams of methylamine gas was substituted for the n-butylamine. The product yield was 3.8 grams, mp. 81-83" C.

Other compounds were made in a similar manner using appropriate starting materials. The compounds are listed in Table I.

TABLEI Example 9 S OH u/ SnSP s NHCHzCHsCHg snsi CH; 3 ON=C CH; S 2 5 S115 CHzCH- CHg a N CHgGH=CHg 40 mg a N 15----::.. S cgHg 6 TABLE I Continued TABLE I-Continued Example Example 20 S CgH5 34 fi/C H SnS i omon=om r SnSP\ on, a a 3 NHCH .u-u-TJ-I 2 5 (@l (6) 115 NHCHgCH=CHz S 0mm INSECTICIDAL EVALUATION TESTS The following insect species are subjected to evaluation 22 fi tests for insecticidal activity.

(0) K S 1 Housefly (HF)Musca domestica (Linn) 1 (2 Lygus Bug (LB)-Lygus hesperus (Knight) N (3 Bean Aphid (BA)Aphisfabae (Scop.)

(4) Two-spotted Mite (21$M)Tetranychus urticae 23 H/CZH'I' (Koch) SnSP (5) Salt-Marsh Caterpillar (SMC)-Estigmene acrea O-N=CHCH: y)

(6) Beet armyworm (BAW)Sp0d0ptera exz'gua (Hub- 24 fi ner) s s P (7) Tobacco budworm (TBW)-Heli0this virescens (Fabnncmcmcrnofl mm) 25 s 01H Aliquots of the toxicants, dissolved in an appropriate ll solvent, are diluted in water containing 0.018% of a wet- H ting agent, Sponto 221 (a polyoxyether of alkylated OCH2CH2NHCCH: phenols blended with organic sulfonates). Test concentrac H tions range from 0.1% downward to that at which 50% 26 H 2 5 mortality is obtained. In the tests, for these species, ten SHSP CH3 l-month old nymphs of the Lygus Bug are placed in a circular cardboard cage sealed on one end with cello- CH3 CH3 phane and covered by a cloth netting on the other. Test concentrations for the Lygus Bug ranged from 0.05% 27 S 09115 9 downward to that at which 50% mortality was obtained. il CH3 Each of the aqueous suspensions of the candidate coma pounds are sprayed onto the insects through the cloth net- NHCHZCHZCH ting by means of a hand spray gun. Percent mortality in CH3 each case is recorded after 72 hours, and the LD value expressed as percent of toxicant in the aqueous spray is 28 fi recorded. The results are in Table II under Column LB. snSP 02115 The following procedure is used to test housefiies: A \NHCH stock solution containing 0.1 percent by weight of the C H toxicant in an appropriate solvent is prepared. Aliquots of 5 this solution are combined with 1 milliliter of an acetone- 29 g ,11 peanut oil solution in a 60 mm. O.D. aluminum pan and ll/ allowed to dry. The aliquots are selected to achieve de- 3 sired toxicant concentration ranging from 100 ,ug. per alu- NHCHFQQ minum pan to that at which 50% mortality was attained. The aluminum pan sare placed in a circular cardboard 30 S z a cage, closed on the bottom with cellophane and covered snsr on top with cloth netting. Twenty-five female housefiies a H-CE are introduced into the cage and the percent mortality is recorded after 48 hours. The LD values are expressed in terms of ,ug. per 25 female flies. LD values obtained 31 8 2 in the above-mentioned housefly .test are found in Table i II under Column HF. a The compound is dissolved in the appropriate solvent and diluted to a concentration of 0.1 percent with water containing 0.018% Sponto 221. A portion of the leaf from a bitter dock (Rumex obtusifolius) plant is im- 32 mersed in the test solution for 10 seconds and allowed to n P dry. When dry, the leaf is placed in a Petri dish containing \NHCHK a 9 cm. disc of moistened filter paper. Five 3rd-instar salt- 0 7O marsh caterpillar larvae are placed on the treated leaf. Mortality is recorded after 72 hours. Test concentrations 33 fi range from 0.1 percent to that at which 50% mortality S118? is obtained. This latter concentration is recorded as the a F LD value for the test compound.

CH O 75 The test method for the cotton bollworm, beet armyworm and tobacco budworm is identical to the above except that Romaine lettuce (Lactuca satz'va) is used as the test plant rather than bitter dock.

The compounds are also active against two-spotted mite (Z-SM) Tetranychus urticae (Koch). Pinto bean plants (Plzaseolus sp.) are utilized as the host plant and infested with 50 to 75 mites of various ages. Twenty-four hours after infestation, they are sprayed to the point of run off with aqueous suspension of the toxicant. Test concentrations range from 0.05% to that at which 50% mortality is obtained. The values obtained in this test are found in Table H under the Columns 2SM-PE and ZSM-Eggs.

The compounds are also active against bean aphid (Aplzis fabae (Scop.)) as a contact toxicant. The same test procedure as given for the two-spotted mite above is used for the bean aphid except nasturtium T ropaeolum Sp.) plants approximately 2 to 3 inches tall are used as the host plant. The LD values obtained for the compounds of this invention are found in Table 11 under Column BA.

The compounds of this invention are generally embodied into a form suitable for convenient application. For example, the compounds can be embodied into pesticidal compositions which are provided in the form of emulsions, suspensions, solutions, dusts and aerosol sprays. In general, such compositions will contain, in addition to the active compound, the adjuvants which are found normally in pesticide preparations. In these compositions, the active compounds of this invention can be employed as the sole pesticide component or they can be used in admixture with other compounds having similar utility. The pesticide compositions of this invention can contain, as adjuvants, organic solvents, such as sesame oil, xylene range solvents, heavy petroleum, etc.; water; emulsifying agents; surface active agents; talc; pyrophyllite; diatomite; gypsum; clays; propellants, such as dichlorodifiuoromethane, etc. If desired, however, the active compounds can be applied directly to feedstuffs, seeds, etc. upon which the pests feed. When applied in such a manner, it will be advantageous to use a compound which is not volatile. In connection with the activity of the presently disclosed pesticidal compounds, it should be fully understood that it is not necessary that they be active as such. The purposes of this invention will be fully served if the compound is rendered active by external influences, such as light or by some physiological action which occurs when the compound is ingested into the body of the pest.

The precise manner in which the pesticidal compositions of this invention are used in any particular instance will be readily apparent to a person skilled in the art. Generally, the active pesticide compound will be embodied in the form of a liquid composition; for example, an emulsion, suspension, or aerosol spray. While the concentration of the active pesticide in the present compositions can vary within rather wide limits, ordinarily the pesticide compound will comprise not more than about 50.0% by weight of the composition. Preferably, however, the pesticide compositions of this invention will be in the form of spray tank solutions or suspensions containing about 0.1 to 1.0% by Weight of the active pesticide compound.

What is claimed is:

1. A composition of matter consisting of the formula orb-CH,

CH, CHI-CH:

CH$CH2 fi/R;

CH-Sn-S-P CHz-CH:

CHI-C13 CH, C

Clix-C wherein R is lower alkyl having 1 to 4 carbon atoms, and R can be selected from alkylketoximino, cycloalkylketoximino, alkylaldoximino, alkylcarbamylalkoxy, and

and

CzHg N/ CzHs 5. A composition of Claim 1 wherein R is C H 6. A composition of Claim 1 wherein R is C H R2 iS 7. A composition of Claim 1 wherein R is C H R2 is and and

and

O NHNH OCHa:

8. A composition of Claim 1 wherein R is C H R3 is NHCH2CH2CH2CH3.

9. A composition of Claim 1 wherein R is C H R2 iS NHCH 10. A composition of Claim 1 wherein R is C H R is NHCH CH CH and and

and

11. A composition of Claim 1 wherein R is C H and R2 is /CHa ON=C 12. A composition of Claim 1 wherein R is C H and R2 is CHQCH=CH3 N\ CHzGH=CH 13. A composition of Claim 1 wherein R is C H and R2 is 14. A composition of Claim 1 wherein R is C 11 and R2 is NHCHzQ;

15. A composition of Claim 1 wherein R is C H and R2 is /CH2CH2CN N \CHQCHZCN 16. A composition of Claim 1 wherein R is C H and R2 is 17. A composition of Claim 1 wherein R is C H and R2 is cmcmocm N CHICHQOCHZ 18. A composition of Claim 1 wherein R is C H and R2 is NEE-@CzHa;

19. A composition of Claim 1 wherein R is C H and R2 is N CHa I 20. A composition of Claim 1 wherein R is C H and R2 is CHOH=CH1 21. A composition of Claim 1 wherein R is C H and R2 is S OzNHz 10 22. A composition of Claim 1 wherein R is C H and R is O--N=CHCH 23. A composition of Claim 1 wherein R is C H and R2 is 24. A composition of Claim 1 wherein R is C H and R3 is R2 is imam-Q01.

29. A composition of Claim 1 wherein R is C H and R2 is (CHCH2CH3) 30. A composition of Claim 1 wherein R is C H and R2 is CH: NHC

31. A composition of Claim 1 wherein R is C H and R is NHCH CH=CH References Cited UNITED STATES PATENTS 3,542,824 11/ 1970 Bublitz 260-4297 3,546,240 12/1970 Bublitz 260429.7 3,565,860 2/1971 Pande 260429.7 3,591,614 7/ 1971 Bublitz 260'429.7 3,598,849 8/1971 Bublitz 260-429] 3,641,037 2/ 1972 Bublitz 260-429] 3,674,789 7/1972 Bublitz 260429.7

DANIEL E. WYMAN, Primary Examiner A. P. DEMERS, Assistant Examiner US. Cl. X.R. 

